We show that reduced rhenium bipyridyl carbonyl complexes are stable and selective catalysts for deoxygenation of nitrous oxide (N 2 O) in organic media in the presence of water. Mechanistic studies indicate that the Re complex is initially reduced to produce the activated species. N 2 O then binds to labile position at the reduced metal and the resulting adduct is further reduced to trigger N–O bond breaking and release of N 2 . Proton donors are beneficial to enhance the catalytic rate and to reduce the energy required to generate potential limiting intermediate. These results open directions for N–O bond activation.